CN102628131A - Aluminum lutecium ytterbium alloy and method for preparing same through molten salt electrolysis - Google Patents
Aluminum lutecium ytterbium alloy and method for preparing same through molten salt electrolysis Download PDFInfo
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- CN102628131A CN102628131A CN2012101227954A CN201210122795A CN102628131A CN 102628131 A CN102628131 A CN 102628131A CN 2012101227954 A CN2012101227954 A CN 2012101227954A CN 201210122795 A CN201210122795 A CN 201210122795A CN 102628131 A CN102628131 A CN 102628131A
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Abstract
The invention provides an aluminum lutecium ytterbium alloy and a method for preparing same through molten salt electrolysis. The method includes the following steps of: In an electrolytic furnace, using AlF3, NaCl, KCl and KF as an electrolyte system with the mass ratio of AlF3 to NaCl to KCl to KF being 6.7-12.6%:36.5-38.9%: 46.9-50.1%:3.8-4.1%, adding Lu2O3 powder and Yb2O3 powder to the electrolyte system ,the amount of the added Lu2O3 and Yb2O3 both being 5.3 to 10.2% of the weight of AlF3, heating an obtained mixture to the temperature from 750 DEG C to 850 DEG C until the mixture melts, and carrying out electrolysis on the obtained melted substance for 2 to 4 hours with metal molybdenum acting as a cathode, graphite acting as an anode, electrolysis temperature being 750 DEG C to 850 DEG C, cathode current density being 2.8 to 7.8 A/cm<2>, anode current density being 0.5A/cm<2> and cell voltage being 4.1 to 5.3V, to obtain aluminum lutecium ytterbium alloy precipitated near the cathode of a molten salt electrolysis cell, with the contents of aluminium, lutecium and ytterbium respectively being 71.1 to 96.6%, 2.3 to 18.8% and 0.9 to 10.4%. The method provided in the invention can prolong service life of equipment, save energy and reduce production cost.
Description
Technical field
The present invention relates to is a kind of rare earth aluminium alloy.The present invention also relates to a kind of preparation method of rare earth aluminium alloy.Specifically be a kind of method that in the fluorochloride molten salt system, prepares aluminium lutetium ytterbium ternary alloy.
Background technology
It is little that aluminium and alloy thereof have proportion, and specific tenacity is high, corrosion-resistant, good processability, is easy to characteristics such as moulding.Along with the development of modern industrial technology, aluminium and alloy thereof become indispensable important materials the sixth of the twelve Earthly Branches, have a wide range of applications at aspects such as hi-tech, national defence, light industry, building, power communication, communications and transportation.Along with science and technology development, to the demands for higher performance of aluminium and alloy thereof.In order to improve the performance of aluminium and alloy thereof, on melting and complete processing thereof, improve on the one hand, in aluminium and alloy thereof, add other elements on the other hand.Rare earth is the effective additive in the metallurgical industry; REE adds in aluminium and the alloy thereof as trace element; The metamorphism of crystal grain thinning is not only arranged; Improve the effect of castability, mechanical property, enhancing alloy corrosion resistance and the alloy creep performance of alloy in addition, thereby can significantly improve the over-all properties of aluminium and alloy thereof.
Compare with adding light rare earths, in alloy, add heavy rare earth element and have remarkable advantages more, this be because: 1) solid solubility of heavy rare earths in alloy is bigger, and solid solubility sharply descends along with the reduction of temperature; 2) heavy rare earths has good solution strengthening and precipitation strength effect.
Al-Lu (Yb) alloy has widely to be used.Lutetium and alloy thereof are widely used in the preparation of ground such as magneticsubstance, superconducting material and luminescent material.In addition, the metal lutetium can be made lutetium aluminium probe tile, is used for the neutron probe of nuclear reactor.Simultaneously, in duraluminum, add rare earth element y b, can form the spherical disperse phase that contains Yb and suppress recrystallize effectively, significantly improve the anti-stress corrosion performance of alloy.
At present, domestic preparation Al rare earth alloy mainly is to adopt method of mixing (consolute is sent out) and fused salt electrolysis process.To mixing the method advantage be: equipment is simple, and is convenient and easy, can in aluminium liquid, directly add rare earth metal and prepare alloy aluminum liquid.Shortcoming is: composition is wayward, during use, and the instability of producing effects in fact, end product quality should not guarantee; Production Flow Chart is long, complex process, and power consumption is high, and alloying constituent is prone to segregation, and production cost is high.
Fused salt electrolysis process can be divided into electrolysis of fused chloride salt and fluorochemical-oxide and salt melt electrolyzing again.Two kinds of methods respectively have relative merits.It is less that the electrolysis of fused chloride salt method has fused salt corrosion property, easy master, and the structured material of large scale electrolytic cell solves easily, therefore is the basic skills that modern rare earth electrolytic industry is produced rare earth metal.But the preparation cost of rare earth chloride is high, dehydration difficulty and reactive behavior are high, the accumulating difficulty.Fluorochemical-oxide electrolysis method has the advantage of the good accumulating of oxide compound, but with respect to the molten chloride system, the fusing point of fluorochemical-oxide compound fused salt is higher, and electrolysis temperature is high, and fused salt corrosion property is strong.The maximum characteristics of two kinds of electrolysis process are: can handle dystectic rare earth metal, and as long as constantly replenish rare earth oxide, electrolysis just can be carried out continuously.Fused salt electrolysis process because can work continuously, equipment is simple, economical convenient, not limited by reductive agent, be widely used for producing macro-mixing rare earth metal and part single rare earth metal and rare earth alloy.
In the prior art relevant for the report that adopts fused salt electrolysis process direct production Al rare earth alloy; For example one Chinese patent application number is 200410002122.0; Name is called and discloses a kind of pure zirconia cerium that in aluminium cell, adds in " method that fused salt electrolysis process directly prepares aluminium cerium master alloy "; Electrolysis temperature is 940～965 ℃, reacts through fused salt electrolysis, makes cerium in electrolytic process, directly dissolve in the method for the production aluminium cerium master alloy of aluminium liquid.This rare earth alloy contains the cerium more than 10%.Directly to prepare duraluminum close with fused salt electrolysis process, and publication number is that the characteristics of disclosed in the CN1410599 patent document " a kind of method of electrolysis production aluminum scandium alloy " are: utilize fine aluminium, Sc
2O
3And molten salt system (NF
4HF, NaF, KCl, NaCl, sodium cryolite and potassium cryolite) electrolysis temperature is 950 ± 20 ℃, preparation Al
3The Sc alloy.One Chinese patent application number is 03153786.3 patent document report; In cryolite-based system, add 1～6% aluminum oxide, 0.1～8% Scium trioxide, 0.1～2% zirconium white; 900～990 ℃ of electrolysis temperatures; Can make the aluminium, Seandium, zirconium master alloy through the electrolysis eutectoid, wherein scandium content is 0.1～3%.For example directly preparing the close name of duraluminum with fused salt electrolysis process again is called in the patent document of " a kind of rare earth aluminium alloy and preparation method thereof and device " (publication number is CN101724769A), with REF
3, sodium aluminum fluoride nNaFAlF
3, lithium fluoride LiF is electrolyte system, electrolysis temperature is 850～1100 ℃, can obtain Al rare earth alloy through electrolysis, contains at least a rare earth metal in lanthanum, cerium, praseodymium, neodymium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, lutetium, scandium, the yttrium in the alloy.
Summary of the invention
The object of the present invention is to provide a kind of employing metallic compound is raw material, lets the ion of aluminium, lutetium, the ytterbium direct aluminium lutetium ytterbium alloy of preparation of coelectrodeposition on negative electrode.The present invention also aims to provide the fused salt electrolysis preparation method thereof of the aluminium lutetium ytterbium alloy that a kind of technology is simple, energy consumption is low.
Aluminium lutetium ytterbium alloy of the present invention is that aluminium 71.1～96.6%, lutetium 2.3～18.8%, ytterbium 0.9～10.4% are formed by weight ratio.
The fused salt electrolysis preparation method thereof of aluminium lutetium ytterbium alloy of the present invention is: in electrolytic furnace, with AlF
3+ NaCl+KCl+KF is an electrolyte system, and each electrolytical quality proportioning is AlF
3: NaCl: KCl: KF=6.7～12.6%: 36.5～38.9%: 46.9～50.1%: 3.8～4.1%, with Lu
2O
3And Yb
2O
3Powder adds in the electrolyte system, Lu
2O
3And Yb
2O
3Add-on be AlF
35.3～10.2% of weight is heated to 750～850 ℃ of fusions, is negative electrode with the metal molybdenum, and graphite is anode, 750～850 ℃ of electrolysis temperatures, and cathode current density is 2.8～7.8A/cm
2, anodic current density is 0.5A/cm
2, bath voltage 4.1～5.3V, the electrolysis through 2～4 hours deposits the content that obtains aluminium, lutetium, ytterbium and is respectively: 71.1～96.6%, 2.3～18.8%, 0.9～10.4% aluminium lutetium ytterbium alloy near the fused-salt bath negative electrode; Current efficiency 30.1～75.6%.
NaCl in the electrolyte system, KCl are respectively 300 ℃, 600 ℃ dryings 24 hours.
It is simple to the invention provides a kind of technology, the preparation method of the aluminium lutetium ytterbium ternary alloy that production cost is low.Its characteristics are: (1) both without metallic aluminium, also without rare earth metal, but adopts the fluoride salt of aluminium; The oxide compound of rare earth is a raw material, adopts fused salt electrolysis directly to prepare aluminium lutetium ytterbium alloy, and realization lutetium, the electrolysis of ytterbium in fused salt are separated out; Production Flow Chart is shortened greatly, and technology is simple.(2) electrolysis temperature of the present invention low (750～850 ℃) is well below Lu
2O
3Fusing point (2490 ℃) and Yb
2O
3Fusing point (2372 ℃), therefore, can prolong the work-ing life of equipment, save the energy, reduce production costs.
The present invention adopts AlF
3+ NaCl+KCl+KF is electrolytical fluorine chlorination system, compatible electrolysis of fused chloride salt method and the advantage of fluorochemical-oxide and salt melt electrolyzing method in the fused salt electrolysis, and in addition, a spot of KF can avoid the negative electrode passivation in the molten salt system.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 gained alloy.
Fig. 2 is the XRD figure spectrum of embodiment 3 gained alloys.
Embodiment
It is following that fused salt electrolysis prepares the concrete technical process of method of aluminium lutetium ytterbium alloy:
(1) NaCl, KCl be respectively 300 ℃, 600 ℃ dryings 24 hours, and the dehydration back that finishes is NaCl: KCl=35 with the mass ratio: 45 ratio mixes NaCl and KCl, with KF, AlF
3, Lu
2O
3And Yb
2O
3Powder directly joins in the molten salt system, mixes, and wherein KF is 3.5～4g, AlF
3Be 6～12g, Lu
2O
3And Yb
2O
3Add-on is AlF
35.3～10.2% of quality.
(2) definite as required electrolysis temperature, electrolysis time and current density are carried out electrolysis.Can lead to argon gas protection in the electrolytic process.
For example the present invention is done in more detail below and describes:
Embodiment 1: in electrolytic furnace, with AlF
3+ NaCl+KCl+KF is an electrolyte system, with Lu
2O
3And Yb
2O
3Powder adds in the molten salt system, is heated to 780 ℃ of fusions, and each electrolytical quality proportioning is AlF in the system
3: NaCl: KCl: KF=10.6%: 37.2%: 47.9%: 4.3%, Lu
2O
3And Yb
2O
3Add-on be AlF
38.8% of weight; With metal molybdenum (Mo) is negative electrode, and graphite is anode, 780 ℃ of electrolysis temperatures, and cathode current density is 6.4A/cm
2, anodic current density is 0.5A/cm
2, bath voltage 4.1-4.3V, the electrolysis through 3.2 hours deposits the Al-Lu-Yb ternary alloy near the fused-salt bath negative electrode, and the content of aluminium, lutetium, ytterbium is respectively: 76.4%, 13.2%, 10.4%, current efficiency is 52.9%.
Embodiment 2: in electrolytic furnace, with AlF
3+ NaCl+KCl+KF is an electrolyte system, with Lu
2O
3And Yb
2O
3Powder adds in the molten salt system, is heated to 850 ℃ of fusions, and each electrolytical quality proportioning is AlF in the system
3: NaCl: KCl: KF=12.5%: 36.5%: 46.9%: 4.1%, Lu
2O
3And Yb
2O
3Add-on be AlF
35.3% of weight; With metal molybdenum (Mo) is negative electrode, and graphite is anode, 850 ℃ of electrolysis temperatures, and cathode current density is 2.8A/cm
2, anodic current density is 0.5A/cm
2, bath voltage 5.0-5.3V, the electrolysis through 2 hours deposits the Al-Lu-Yb ternary alloy near the fused-salt bath negative electrode, and the content of aluminium, lutetium, ytterbium is respectively: 96.6%, 2.5%, 0.9%, current efficiency is 70.3%.
Embodiment 3: in electrolytic furnace, with AlF
3+ NaCl+KCl+KF is an electrolyte system, with Lu
2O
3And Yb
2O
3Powder adds in the molten salt system, is heated to 750 ℃ of fusions, and each electrolytical quality proportioning is AlF in the system
3: NaCl: KCl: KF=9.1%: 37.9%: 48.7%: 4.3%, Lu
2O
3And Yb
2O
3Add-on be AlF
38.5% of weight; With metal molybdenum (Mo) is negative electrode, and graphite is anode, 750 ℃ of electrolysis temperatures, and cathode current density is 7.8A/cm
2, anodic current density is 0.5A/cm
2, bath voltage 4.8-5.2V, the electrolysis through 3.5 hours deposits the Al-Lu-Yb ternary alloy near the fused-salt bath negative electrode, and the content of aluminium, lutetium, ytterbium is respectively: 91.9%, 4.4%, 3.7%, current efficiency is 30.8%.
Embodiment 4: in electrolytic furnace, with AlF
3+ NaCl+KCl+KF is an electrolyte system, with Y
2O
3And Yb
2O
3Powder adds in the molten salt system, is heated to 800 ℃ of fusions, and each electrolytical quality proportioning is AlF in the system
3: NaCl: KCl: KF=12.6%: 36.6%: 47.1%: 3.8%, Lu
2O
3And Yb
2O
3Add-on be AlF
37.6% of weight; With metal molybdenum (Mo) is negative electrode, and graphite is anode, 800 ℃ of electrolysis temperatures, and cathode current density is 4.7A/cm
2, anodic current density is 0.5A/cm
2, bath voltage 4.1-4.3V, the electrolysis through 4 hours deposits the Al-Lu-Yb ternary alloy near the fused-salt bath negative electrode, and the content of aluminium, lutetium, ytterbium is respectively: 87.5%, 6.7%, 5.8%, current efficiency is 60.4%.
Embodiment 5: in electrolytic furnace, with AlF
3+ NaCl+KCl+KF is an electrolyte system, with Lu
2O
3And Yb
2O
3Powder adds in the molten salt system, is heated to 820 ℃ of fusions, and each electrolytical quality proportioning is AlF in the system
3: NaCl: KCl: KF=6.7%: 38.9%: 50.1%: 4.3%, Lu
2O
3And Yb
2O
3Add-on be AlF
310.2% of weight; With metal molybdenum (Mo) is negative electrode, and graphite is anode, 820 ℃ of electrolysis temperatures, and cathode current density is 4.7A/cm
2, anodic current density is 0.5A/cm
2, bath voltage 4.7-5.0V, the electrolysis through 2 hours deposits the Al-Lu-Yb ternary alloy near the fused-salt bath negative electrode, and the content of aluminium, lutetium, ytterbium is respectively: 93.7%, 4.0%, 2.3%, current efficiency is 30.1%.
Embodiment 6: in electrolytic furnace, with AlF
3+ NaCl+KCl+KF is an electrolyte system, with Lu
2O
3And Yb
2O
3Powder adds in the molten salt system, is heated to 800 ℃ of fusions, and each electrolytical quality proportioning is AlF in the system
3: NaCl: KCl: KF=11.6%: 37.0%: 41.6%: 3.8%, Lu
2O
3And Yb
2O
3Add-on be AlF
36.9% of weight; With metal molybdenum (Mo) is negative electrode, and graphite is anode, 800 ℃ of electrolysis temperatures, and cathode current density is 4.7A/cm
2, anodic current density is 0.5A/cm
2, bath voltage 4.1-4.2V, the electrolysis through 2.5 hours deposits the Al-Lu-Yb ternary alloy near the fused-salt bath negative electrode, and the content of aluminium, lutetium, ytterbium is respectively: 711%, 18.8%, 10.1%, current efficiency is 75.6%.
Claims (3)
1. aluminium lutetium ytterbium alloy is characterized in that by weight ratio being that aluminium 71.1～96.6%, lutetium 2.3～18.8%, ytterbium 0.9～10.4% are formed.
2. the fused salt electrolysis preparation method thereof of an aluminium lutetium ytterbium alloy is characterized in that: in electrolytic furnace, with AlF
3+ NaCl+KCl+KF is an electrolyte system, and each electrolytical quality proportioning is AlF
3: NaCl: KCl: KF=6.7～12.6%: 36.5～38.9%: 46.9～50.1%: 3.8～4.1%, with Lu
2O
3And Yb
2O
3Powder adds in the electrolyte system, Lu
2O
3And Yb
2O
3Add-on be AlF
35.3～10.2% of weight is heated to 750～850 ℃ of fusions, is negative electrode with the metal molybdenum, and graphite is anode, 750～850 ℃ of electrolysis temperatures, and cathode current density is 2.8～7.8A/cm
2, anodic current density is 0.5A/cm
2, bath voltage 4.1～5.3V, the electrolysis through 2～4 hours deposits the content that obtains aluminium, lutetium, ytterbium and is respectively: 71.1～96.6%, 2.3～18.8%, 0.9～10.4% aluminium lutetium ytterbium alloy near the fused-salt bath negative electrode.
3. the fused salt electrolysis preparation method thereof of aluminium lutetium ytterbium alloy according to claim 2 is characterized in that: the NaCl in the electrolyte system, KCl are respectively 300 ℃, 600 ℃ dryings 24 hours.
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|---|---|---|---|
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|---|---|---|---|
| CN2012101227954A CN102628131B (en) | 2012-04-24 | 2012-04-24 | Aluminum lutecium ytterbium alloy and method for preparing same through molten salt electrolysis |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724769A (en) * | 2008-10-13 | 2010-06-09 | 北京有色金属研究总院 | Rare earth aluminum alloy, and method and device for preparing same |
| CN101906604A (en) * | 2010-07-30 | 2010-12-08 | 江苏中矿大正表面工程技术有限公司 | Rare earth aluminum alloy wire for thermal spraying |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724769A (en) * | 2008-10-13 | 2010-06-09 | 北京有色金属研究总院 | Rare earth aluminum alloy, and method and device for preparing same |
| CN101906604A (en) * | 2010-07-30 | 2010-12-08 | 江苏中矿大正表面工程技术有限公司 | Rare earth aluminum alloy wire for thermal spraying |
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